JPH0687993A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in fluidity in molding and excellent in impact resistance and delamination under high shearing stress. CONSTITUTION:The objective thermoplastic resin composition contains 1-99 pts.wt. thermoplastic resin other than an olefinic resin and 99-1 pts.wt. modified olefinic resin and contains 0.1-50 pts.wt. compatibilizer based on 100 pts.wt. base resin. The compatibilizer is a reactional product consisting of 5-95 pts.wt. modified olefinic polymer and 95-5 pts.wt. modified vinyl chloride polymer. The modified olefinic polymer has one structural unit having each at least one reactional group selected from an amide group, a glycidyloxy group and/or a glycidyl group. The modified vinyl chloride polymer contains a compound having a group reactive to a reactional group which the modified olefinic polymer has in a ratio of 0.05-50wt.% as a copolymer component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent fluidity during molding, impact resistance of molded articles, and surface layer peeling resistance under high shear.

[0002]

2. Description of the Related Art Recently, it has been actively studied to modify a resin by mixing (alloying) polymers having different properties. For example, there are the following reports on a method of mixing an olefin resin and a styrene resin or a vinyl chloride resin. That is, a method of mixing an ethylene-vinyl acetate copolymer with an olefin resin (JP-B-60-36178) and a method of mixing a polyethylene-EPDM modified product with an olefin resin (JP-A-63-304039, JP-A-1-30439). 165640), and a method of mixing a block body of polypropylene and styrene resin with an olefin resin (JP-A-2-19912).
7, JP-A-2-199128, JP-A-2-19912
9) and the like.

[0003]

SUMMARY OF THE INVENTION In the above conventional method,
The flowability during molding is poor, the impact resistance of the molded product decreases, and after molding under high shear such as injection molding, the surface layer of the molded product peels off with a slight force. To be Therefore, it has a drawback that it is difficult to put it into practical use.

The present invention solves the above drawbacks.
It is an object of the present invention to provide a thermoplastic resin composition which has excellent fluidity at the time of molding, impact resistance of a molded article, and excellent surface layer peeling resistance under high shear.

[0005]

The thermoplastic resin composition of the present invention comprises a thermoplastic resin (X) 1 other than an olefin resin.
~ 99 parts by weight and modified olefin resin (C) 99-1
A composition containing 0.1 to 50 parts by weight of a compatibilizer (Y) per 100 parts by weight of a base resin containing 100 parts by weight,
The compatibilizer (Y) is the modified olefin polymer (D) 5
~ 95 parts by weight and modified vinyl chloride polymer (E) 95 ~
5 parts by weight of the olefin polymer (D) is a olefin repeating unit 2 to 100.
The modified vinyl chloride polymer (E) contains one structural unit having at least one amide group and at least one reactive group selected from the group consisting of a glycidyloxy group and a glycidyl group per 0. The compound having a group having a reactive group with the reactive group of the olefin polymer (D) is contained as a copolymerization component in an amount of 0.05 to 50% by weight, whereby the above object is achieved.

The present invention will be described in detail below.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin (X) other than an olefin resin as a base resin.
And a modified olefin resin (C).

Examples of the thermoplastic resin (X) other than the olefin resin contained in the resin composition of the present invention include vinyl chloride resin, styrene resin, polyester resin, polycarbonate resin, polyamide resin, and polyphenylene ether resin. Is mentioned. Of these, vinyl chloride resin (A) and styrene resin (B) are preferable.

The vinyl chloride resin (A) used in the present invention is preferably a resin having an average degree of polymerization of 400 to 1500, more preferably 450 to 1000. If the average degree of polymerization is less than 400, the impact resistance will decrease, while if it exceeds 1500, the fluidity at the time of molding will tend to significantly decrease, such being undesirable. Examples of the vinyl chloride resin (A) include a homopolymer of vinyl chloride, a copolymer containing vinyl chloride in a proportion of 80% by weight or more, and post-chlorinated polyvinyl chloride. In addition to vinyl chloride, the components of the copolymer include monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. These compounds may be contained in the copolymer in a total amount of 20% by weight or less. The above homopolymer and copolymer may be contained alone or in combination of two or more.

Styrene resin (B) used in the present invention
As, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-styrene-α-methylstyrene copolymer, ABS
Resin, AS resin, MABS resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-butadiene-styrene-α-
Methyl styrene copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N
-Substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer, acrylonitrile-
Examples thereof include a butadiene-styrene-β-isopropenylnaphthalene copolymer, an acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene-maleimide copolymer and the like. These may be contained alone or in combination of two or more. In order to prevent deterioration of the surface layer peeling resistance of the molded product, a resin compatible with the vinyl chloride resin is preferable.

The styrenic resin (B) is 40 to 90% by weight of a rubbery polymer (described later) and a predetermined monomer mixture 6
It is preferable that the graft copolymer obtained by polymerizing 0 to 10% by weight is contained in a proportion of 0 to 70 parts by weight. The monomer mixture is composed of at least one compound selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds, alkyl methacrylate compounds, and monomers copolymerizable with the compounds. By using the styrene resin (B), a molded article having excellent impact resistance can be obtained.

The rubber-like polymer used in the styrene resin (B) includes polybutadiene rubber and styrene-
Examples thereof include butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and butyl acrylate rubber. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the aromatic vinyl compound include styrene, methylstyrene, chlorostyrene, α-methylstyrene and the like.
Furthermore, examples of the alkyl methacrylate compound include methyl methacrylate and ethyl methacrylate. The above polymers and compounds may be contained alone or in combination of two or more.

The methyl ethyl ketone soluble component of the styrene resin (B) contains, as a copolymerization component, at least one compound selected from vinyl cyanide compounds and alkyl methacrylate compounds in a proportion of 10 to 60% by weight. It is preferable that the content is 15 to 60% by weight. If the content of the above compound is less than 10% by weight, the resistance to peeling of the surface layer is lowered, while if it exceeds 60% by weight, the fluidity at the time of molding tends to be lowered, such being undesirable. The reduced viscosity of the methyl ethyl ketone soluble component is preferably 0.2 to 0.9 dl / g (dimethylformamide solution, 30 ° C., concentration 0.3 g / dl), more preferably 0.25 to 0.8 dl / g. It is g. When the reduced viscosity is less than 0.2 dl / g, the impact resistance decreases, while on the other hand,
If it exceeds 9 dl / g, the fluidity at the time of molding tends to deteriorate, and the thermal stability tends to deteriorate, which is not preferable. In order to obtain a thermoplastic resin having excellent heat resistance, it is preferable that the methyl ethyl ketone soluble component contains α-methylstyrene in a proportion of 30% by weight or more.

The vinyl chloride resin (A) and the styrene resin (B) may be contained individually,
Alternatively, two or more kinds may be contained.

The modified olefin resin (C) contained in the resin composition of the present invention is a resin in which a reactive group is introduced into the olefin resin. Examples of the olefin resin as the raw material of the modified olefin resin (C) include high density polyethylene, medium density polyethylene, low density polyethylene, and copolymers of ethylene and other α-olefins;
Polypropylene, copolymers of propylene and other α-olefins; polyolefins or oligomers such as polybutene and poly-4-methylpentene-1; ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer Examples thereof include polyolefin elastomers such as polymer, butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylic acid ester copolymer. Each of these polymers may be contained alone or in combination of two or more. Among these polymers, in order to obtain a thermoplastic resin having excellent impact resistance and heat resistance, low density polyethylene, polypropylene, or a copolymer of propylene and another α-olefin is preferable, Polypropylene, or propylene and other α-
Copolymers with olefins are more preferred.

The modified olefin resin (C) preferably has a glycidyloxy group or a group reactive with the glycidyl group contained in the modified olefin polymer (D) in the compatibilizer described later. Further, it is more preferable that the compatibilizing agent described later contains a group reactive with the reactive group contained in the modified vinyl chloride polymer (E). Examples of such a reactive group include an epoxy group, an amino group, an amide group, a carboxyl group and a hydroxyl group. Of these, epoxy groups reactive with carboxyl groups;
Alternatively, an amino group, a carboxyl group, or a hydroxyl group reactive with a glycidyl group is preferable, and an epoxy group or a carboxyl group is more preferable. These reactive groups may be contained in the modified olefin resin (C) alone or in combination of two or more kinds. Acid anhydrides can also be utilized, as can compounds with these reactive groups.

The method for introducing the compound having a reactive group or the acid anhydride into the modified olefin resin (C) is not particularly limited and may be copolymerization or graft polymerization. The content of these reactive groups is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the monomer capable of forming the modified olefin resin (C).

As the monomer or acid anhydride having the above-mentioned reactive group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide. , Acrylic acid, methacrylic acid,
Maleic acid, maleic anhydride, allyl alcohol, 2-
Examples thereof include hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate.

The three-dimensional structure of the modified olefin resin (C) is not particularly limited, but in order to obtain a thermoplastic resin having excellent heat resistance, 60% by weight of isotactic resin is used.
It is preferably contained in the above proportion, and more preferably in a proportion of 70% by weight or more.

The modified olefin resin (C) has a weight average molecular weight of 5,000 to 10,000 in order to obtain a thermoplastic resin having excellent impact resistance and fluidity during molding.
00 is preferable, and 10,000 to 700,000 is more preferable.

The base resin in the thermoplastic resin composition of the present invention is a thermoplastic resin (X) 1 other than the above-mentioned olefin resin.
~ 99 parts by weight, and the modified olefin resin (C) 99
~ 1 part by weight. When the vinyl chloride resin (A) and the styrene resin (B) are used as the thermoplastic resin (X) other than the olefin resin,
These proportions are preferably 10 to 99 parts by weight of the vinyl chloride resin (A) and / or styrene resin (B) and 90 to 1 part by weight of the modified olefin resin (C). More preferably, vinyl chloride resin (A)
And / or the styrene resin (B) is 10 to 70 parts by weight, and the modified olefin resin (C) is 90 to 30 parts by weight.

For the preparation of the vinyl chloride resin (A), the styrene resin (B), and the modified olefin resin (C), known methods can be used, respectively.
The operation is not particularly limited. After preparation, the base resin in powder or pellet form is obtained by known methods.

The thermoplastic resin composition of the present invention contains a compatibilizing agent (Y) in the above base resin.

The compatibilizer (Y) used in the present invention is a reaction product of the modified olefin polymer (D) and the modified vinyl chloride polymer (E).

The modified olefin polymer (D) is an olefin polymer modified with a specific compound. Examples of the olefin polymer as a raw material of the modified olefin polymer (D) include homopolymers of various olefin monomers, random copolymers thereof, block copolymers thereof or graft copolymers thereof, or , And a mixture of these homopolymers or copolymers.
For example, high density polyethylene, medium density polyethylene, low density polyethylene, copolymers of ethylene and other α-olefins; polypropylene, copolymers of propylene and other α-olefins; polybutene, poly-4-
Polyolefins or oligomers such as methylpentene-1; ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer,
Examples thereof include polyolefin elastomers such as butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylic acid ester copolymer. These polymers may be contained alone or in combination of two or more. Among these polymers, in order to obtain a thermoplastic resin having excellent impact resistance and heat resistance, low density polyethylene, polypropylene, a copolymer of propylene and other α-olefin, and these polymers are constituted. Oligomers of monomers are preferred, and polypropylene, copolymers of propylene and other α-olefins, and oligomers of monomers constituting these polymers are more preferred.

The three-dimensional structure of this olefin polymer is not particularly limited, but in order to obtain a thermoplastic resin having excellent heat resistance, it is preferable to contain the isotactic resin in a proportion of 60% by weight or more, More preferably, the content is 70% by weight or more. Further, the molecular weight of the olefin polymer is 500 to 6 on average in order to obtain a thermoplastic resin excellent in impact resistance and fluidity during molding.
0000 is preferable, and 1000 to 50000 is more preferable. The number average molecular weight can be measured using GPC (gel permeation chromatography).

The modified olefin polymer (D) contains at least one amide group and at least one reactive group selected from the group consisting of glycidyloxy group and glycidyl group, per 2-1000 repeating units of olefin. It contains one structural unit.

Such modified olefin polymer (D)
As a method for producing, a compound having a reactive group capable of polymerizing with an olefin (for example, a vinyl group) and having at least one amide group and at least one glycidyloxy group and / or glycidyl group, and an olefin Examples thereof include a method of copolymerizing. Further, a method of producing a polyolefin by an ordinary polymerization method and then graft-polymerizing the above-mentioned compound on the obtained polyolefin chain by an ordinary method can be mentioned. In addition, when copolymerizing or graft-polymerizing the olefin and the above compound,
Examples thereof include a method in which a vinyl monomer other than the compound represented by the general formula (I) is copolymerized with an olefin.

The modified olefin polymer (D) is preferably an olefin polymer modified with a compound represented by the following general formula (I).

[0030]

[Chemical 2]

(In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms and having at least one reactive group selected from the group consisting of a glycidyloxy group and a glycidyl group, and R represents hydrogen. It represents an atom or a methyl group.) The compound represented by the above general formula (I) can be produced, for example, by the method described in JP-A-60-130580. In this method, the compound has the following general formula (I
It can be produced by adding epihalohydrin to the compound represented by I) and then performing a dehydrohalogenation reaction under alkaline conditions.

[0032]

[Chemical 3]

(In the formula, Ar 'represents an aromatic hydrocarbon group having at least one hydroxyl group and having 6 to 23 carbon atoms, and R represents a hydrogen atom or a methyl group.) For example, as a starting material 2,6-xylenol and N-
When methylolacrylamide is used, a compound represented by the following structural formula (III) is obtained.

[0034]

[Chemical 4]

The modified olefin polymer (D) is obtained by copolymerizing the compound represented by the general formula (I) with the olefin polymer. The modified olefin polymer (D) thus obtained has an amide group, a glycidyloxy group and a glycidyl group represented by the following general formula (IV) per 2 to 1000 repeating units of olefin. It is a polymer containing one structural unit having.

[0036]

[Chemical 5]

(In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms and having at least one reactive group selected from the group consisting of a glycidyloxy group and a glycidyl group, and R represents hydrogen. Represents an atom or a methyl group.) When the amount of the structural unit contained in the modified olefin polymer (D) is too small, the modification of the olefin polymer is insufficient, and therefore the resulting composition is used. When it is formed by molding, the surface layer peeling resistance of the molded product cannot be sufficiently obtained. This structural unit is contained in the modified olefin polymer (D) in the form of a random or graft copolymer.

The method for producing a copolymer of the compound represented by the general formula (I) and an olefin polymer is not particularly limited, but the following two methods are preferably used.

The first production method is a method of radically adding an olefin polymer and a compound having a glycidyl group represented by the above general formula (I) using a radical initiator. The reaction is carried out using an ordinary reaction system, but at this time, a solvent which dissolves or swells the olefin polymer can be used. Examples of the solvent include tetralin, decalin, toluene, xylene, and chlorobenzene. Specifically, the compound represented by the general formula (I) and the olefin polymer are melt-kneaded using various conventionally known blenders such as an extruder, a heating roll, a Brabender, and a Banbury mixer. By doing so, the modified olefin polymer (D) is obtained.

The second production method is a method of copolymerizing an olefin monomer and a compound having a glycidyl group represented by the above general formula (I). This copolymerization method is not particularly limited, and examples thereof include a general radical polymerization method, a cationic polymerization method, an anionic polymerization method, and a coordination polymerization method using a transition metal.

The modified olefin polymer (D) produced by the first and second production methods may be a graft copolymer or a block copolymer.

The modified vinyl chloride polymer (E) used in the present invention is a copolymer containing vinyl chloride in a proportion of 50% by weight or more. As the copolymerization component other than vinyl chloride, a compound having a group reactive with the reactive group of the modified olefin polymer (D) (hereinafter referred to as a compound having a reactive group) is 0.05 to 50% by weight. It is contained in the ratio of. Further, as the other copolymerization component, vinyl chloride and another vinyl compound copolymerizable with the compound having the above-mentioned reactive group may be contained in a proportion of 0 to 49.95% by weight.

The reactive group contained in the above-mentioned compound having a reactive group includes an epoxy group, a 1, 2, or a tertiary amino group,
Examples thereof include an amide group, a carboxyl group and a hydroxyl group. When the modified olefin polymer (D) has a glycidyl group, an amino group, a carboxyl group and a hydroxyl group are preferable, and a carboxyl group is more preferable, in order to more effectively carry out the reaction with the glycidyl group.
These reactive groups may be contained individually in the compound having a reactive group, or may be contained as a mixture of two or more kinds. Acid anhydrides can also be utilized, as can compounds with these reactive groups.

Examples of the compound or acid anhydride having the above-mentioned reactive group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acryl. Acid, methacrylic acid,
Maleic acid, maleic anhydride, allyl alcohol, 2-
Examples thereof include hydroxyethyl methacrylate, 2-hydroxyl ethyl acrylate, 2-hydroxyl propyl methacrylate and 2-hydroxyl propyl acrylate.

The proportion of the compound having the above reactive group in the modified vinyl chloride polymer (E) is 0.05 to 50% by weight as described above, preferably 0.1 to 30%.
% By weight. If the proportion of this compound is 0.05% by weight or less, a molded article excellent in surface layer peeling resistance cannot be obtained.
If it exceeds 0% by weight, the fluidity at the time of molding tends to decrease, which is not preferable.

Other vinyl compounds copolymerizable with vinyl chloride and the above-mentioned compound having a reactive group include monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate and butyl acrylate.

The modified vinyl chloride polymer (E) may be a random copolymer, a block copolymer, a graft copolymer, or a mixture of these copolymers. The copolymerization method is not particularly limited, but a general radical polymerization method, cationic polymerization method, anionic polymerization method, coordination polymerization method using a transition metal, or the like can be used.

Examples of the modified vinyl chloride polymer (E) include, as a copolymerization component, vinyl chloride and a compound having a reactive group in a total amount of 80 to 100% by weight, and ethylene. 0 to 20% by weight of monovinylidene compounds such as vinyl acetate, methyl methacrylate, and butyl acrylate (the above "other vinyl compounds")
And a graft copolymer thereof. These compounds may be contained alone or in combination of two or more kinds.
Examples of the other modified vinyl chloride polymer (E) include post-chlorination modified vinyl chloride.

The average degree of polymerization of the modified vinyl chloride polymer (E) is preferably 400 to 1500, and 450 to 10
00 is more preferable. If the average degree of polymerization is less than 400, the impact resistance will decrease, while if it exceeds 1500, the fluidity at the time of molding will significantly decrease, which is not preferable.

The compatibilizer (Y) used in the present invention comprises 5 to 95 parts by weight of the modified olefin polymer (D) and 95 to 5 parts by weight of the modified vinyl chloride polymer (E). It is a reaction product, preferably, the content of the modified olefin polymer (D) is 15 to 85 parts by weight, and the modified vinyl chloride polymer (E) is 85 to 15 parts by weight, more preferably the modified product. The olefin polymer (D) is 25 to 75
The weight of the modified vinyl chloride polymer (E) is 75 to 25 parts by weight. If the amount of the modified olefin polymer (D) is less than 5 parts by weight or more than 95 parts by weight, the effect of compatibility cannot be sufficiently obtained, and thus the surface layer peeling resistance of the molded product is significantly reduced, which is not preferable.

The method for producing the compatibilizer (Y) is not particularly limited, but the glycidyl group of the modified olefin polymer (D) is reacted with the reactive group of the modified vinyl chloride polymer (E). The method can be preferably used. When reacting,
A solvent that dissolves or swells the olefin polymer may be used. Examples of the solvent include tetralin, decalin, toluene, xylene, chlorobenzene and the like. Specifically, the modified olefin polymer (D) and the modified vinyl chloride polymer (E) are melt-kneaded using various conventionally known blenders such as an extruder, a heating roll, a Brabender, and a Banbury mixer. By doing so, the compatibilizer (Y) is obtained.

The compatibilizer (Y) used in the present invention is 0.1 to 50 parts by weight based on 100 parts by weight of the base resin.
It is preferably contained in the composition in a proportion of 1 to 25 parts by weight. If the proportion of the compatibilizing agent (Y) is less than 0.1 parts by weight, a thermoplastic resin having excellent surface layer peeling resistance cannot be obtained. However, it is not preferable because the workability during molding is deteriorated.

As described above, the compatibilizing agent (Y) does not originally have compatibility, for example, between a vinyl chloride resin and / or a styrene resin and an olefin resin, or a compatibilizing agent. It has the effect of improving the compatibility between resins having poor solubility. Therefore, the thermoplastic resin composition of the present invention containing the compatibilizing agent (Y) can provide a molded article having excellent impact resistance and surface layer peeling resistance.

The thermoplastic resin composition of the present invention is obtained by mixing and kneading the base resin obtained by the above method and the powder or pellets of the compatibilizing agent (Y) by a known method. .

The thermoplastic resin composition of the present invention may contain an antioxidant, a heat stabilizer and a lubricant, if necessary, and further, depending on the purpose, a UV absorber, a pigment, an antistatic agent, a flame retardant and a flame retardant. Fuel aids and the like may be included. For example, the composition of the present invention includes a phenolic antioxidant used for styrene resins and olefin resins, a phosphate stabilizer and a tin stabilizer mixed with vinyl chloride resins, and various fatty acid esters thereof. The resin can be used as an injection molding resin by containing an internal / external lubricant such as metal soap and wax.

[0056]

EXAMPLES The present invention will be described below based on examples, but the invention is not limited thereto. In the examples, "part" means part by weight and "%" means% by weight.

(Production of Vinyl Chloride Resins (A-1, A-2)) The vinyl chloride resins used in this example and comparative examples were obtained by a known suspension polymerization method. The degree of polymerization and the chlorine content are shown in Table 1, respectively.

[0058]

[Table 1]

(Production of Styrene Resin (B-1, B-2)) The styrene resin used in this example and comparative examples was obtained by a known emulsion polymerization method. The composition and reduced viscosity of the MEK-soluble component (dimethylformamide solution,
Table 2 shows the results at 30 ° C. and the concentration of 0.3 g / dl).

[0060]

[Table 2]

(Modified olefin resin (C-1 to C-
3)) Table 3 shows the composition of the modified olefin resin used in the examples and comparative examples.

[0062]

[Table 3]

(Production of Modified Olefin Polymer (D-1)) 100 parts of olefin polymer (polypropylene, AH561 manufactured by Union Polymer Co., Ltd.), the following structural formula (II
100 parts of the compound represented by I), and α, α ′-(t
0.1 part of -butylperoxy-m-isopropyl) benzene (Perbutyl P manufactured by NOF CORPORATION) was mixed and dried, and these were supplied to a twin-screw extruder set to 210 ° C.

[0064]

[Chemical 6]

The extrudate thus obtained was cooled with water and pelletized, and then dried at 70 ° C. for 12 hours under reduced pressure to obtain a modified olefin polymer modified polypropylene (D-
1) was obtained.

The obtained dry pellets were crushed and then washed 5 times with acetone to remove unreacted compound and its homopolymer. From the infrared spectrum and the elemental analysis value of the nitrogen atom contained in the resin, the ratio of the weight of the compound of the structural formula (III) into which the modified polypropylene was introduced to the total weight was found to be 37.1%. .

This modified polypropylene had one structural unit derived from the compound of the above structural formula (III) per 11 repeating units of olefin.

(Production of Modified Vinyl Chloride Polymer (E-1)) In an autoclave equipped with a stirrer and a cooler, 250 parts of water, 0.1 part of methyl cellulose, 0.1 part of di-t-butylperoxytrimethyl adipate. Part, and 2-
0.05 parts of mercaptoethanol was charged and the air inside was replaced with nitrogen. To this was charged a mixture of monomers consisting of 95 parts of vinyl chloride and 5 parts of methacrylic acid, and these were polymerized at 50 ° C. for 8 hours.
The unreacted monomer was recovered when the pressure was reduced to / cm ² , and the polymerization was terminated. The obtained polymer slurry was dehydrated and dried to obtain a modified vinyl chloride polymer (E-1).

(Production of Modified Vinyl Chloride Polymer (E-2)) In an autoclave equipped with a stirrer and a cooler, 250 parts of water, 0.1 part of methyl cellulose, 0.1 part of di-t-butylperoxytrimethyl adipate. Part, and 2-
0.05 parts of mercaptoethanol was charged and the air inside was replaced with nitrogen. A mixture of monomers consisting of 90 parts of vinyl chloride, 5 parts of methacrylic acid, and 5 parts of butyl acrylate was charged therein, and these were polymerized at 50 ° C. for 8 hours, and then the pressure was lowered from the steady pressure by 2 kg / cm ² . At this point, unreacted monomer was recovered to terminate the polymerization. The resulting polymer slurry was dehydrated and dried to obtain a modified vinyl chloride polymer (E-2).

(Production of Modified Vinyl Chloride Polymer (E-3)) 250 parts of water, 0.1 part of methyl cellulose, 0.1 part of di-t-butylperoxytrimethyl adipate were placed in an autoclave equipped with a stirrer and a cooler. Part, and 2-
0.05 parts of mercaptoethanol was charged and the air inside was replaced with nitrogen. 100 parts of vinyl chloride was charged into this, and these were polymerized at 50 ° C. for 8 hours, and when the pressure was reduced from the steady pressure by 2 kg / cm ² , unreacted monomers were recovered and the polymerization was terminated. The obtained polymer slurry is dehydrated and dried to give a modified vinyl chloride polymer (E-
3) was obtained.

(Production of Compatibilizer (Y-1 to Y-3)) The modified olefin polymer (D-) obtained as described above.
1) 50 parts and modified vinyl chloride polymer (E-1) 50
Parts were mixed with a Henschel super mixer and dried, and this mixture was fed to a twin-screw extruder set at 160 to 200 ° C. The extrudate obtained was melt-kneaded and pelletized to obtain a compatibilizer (Y-1). Similarly, (D
-1) and (E-2) to (Y-2); and (D-
(Y-3) was obtained from 1) and (E-3).

(Production of compatibilizer (Y-4)) 50 parts of olefin polymer (polypropylene, AH561 manufactured by Union Polymer Co., Ltd.) and modified vinyl chloride polymer (E-
1) 50 parts was mixed with a Henschel super mixer and dried, and this mixture was fed to a twin-screw extruder set at 160 ° C to 200 ° C. Melt kneading the obtained extrudate,
It pelletized and the compatibilizing agent (Y-4) was obtained.

(Measurement of reduced viscosity) Styrene resin (B-
1, B-2) was dissolved in N, N-dimethylformamide to obtain a polymer solution having a concentration of 0.3 g / dl. The passing time (t) at 30 ° C. of the obtained polymer solution was measured according to JIS-K6721 using an Ubbelohde viscometer (capillary viscosity automatic measuring device manufactured by Shibayama Chemical Equipment Co., Ltd.). On the other hand, for the solvent N, N-dimethylformamide, the passage time (t ₀ ) at 30 ° C. was measured using the same device. Using these, the reduced viscosity (η _{r ed} ) was measured by the following formula.

Η _red = (t / t ₀ -1) / C where C represents the concentration (g / dl) of the polymer solution.

The results are shown in Table 2.

(Example 1) As shown in Table 4, 40 parts of vinyl chloride resin (A-1), modified olefin resin (C)
-1) 60 parts, and 10 parts of the compatibilizer (Y-1), and 2 parts of dibutyl tin malate as a stabilizer other than the components shown in Table 4 were mixed using a Henschel mixer.

[0077]

[Table 4]

This mixture was mixed with a twin-screw extruder to obtain 160
The mixture was melt-kneaded at ˜210 ° C. and pelletized to obtain pellets of the thermoplastic resin composition of the present invention.

(Examples 2 to 5) A-1 or A-2 as a vinyl chloride resin and C- as a modified olefin resin.
1 or C-2, and Y-1 or Y as a compatibilizer
-2 was used, and pellets of the thermoplastic resin composition of the present invention were obtained by the same method as in Example 1 except that the contents were changed to those shown in Table 4.

(Example 6) As shown in Table 5, 40 parts of styrene resin (B-1) and modified olefin resin (C-
1) 60 parts and 10 parts of compatibilizer (Y-1) were mixed using a Henschel mixer.

[0081]

[Table 5]

This mixture was mixed with a twin-screw extruder to 200
The mixture was melt-kneaded at ˜250 ° C. and pelletized to obtain pellets of the thermoplastic resin composition of the present invention.

(Examples 7 to 8) B as a styrene resin
-1, or B-2, and Y-1 or Y-2 as the compatibilizer, and the contents of the compositions shown in Table 5, respectively, were used, and the heat treatment of the present invention was carried out in the same manner as in Example 6. Pellets of the plastic resin composition were obtained.

Example 9 As shown in Table 6, 20 parts of vinyl chloride resin (A-1) and styrene resin (B-2).
20 parts, modified olefin resin (C-2) 60 parts, compatibilizer (Y-1) 10 parts, and as a component other than Table 6, dibutyl tin malate 2 parts as a stabilizer, using a Henschel mixer. Mixed.

[0085]

[Table 6]

This mixture was mixed with a twin-screw extruder at 170
The mixture was melt-kneaded at 220 ° C and pelletized to obtain a pellet of the thermoplastic resin composition.

(Examples 10 to 12) A-1 or A-2 was used as the vinyl chloride resin, C-2 was used as the modified olefin resin, and Y-1 or Y-2 was used as the compatibilizer. Pellets of the thermoplastic resin composition were obtained by the same method as in Example 9 except that the content of the composition shown in was used.

Comparative Examples 1 to 6 A-1 as a vinyl chloride resin and C-1 or C-as a modified olefin resin.
3, and Y-1, Y-3 or Y-4 as a compatibilizer
Was used, and pellets of the thermoplastic resin composition were obtained in the same manner as in Example 1 except that the contents were changed to those shown in Table 4.

(Comparative Examples 7 to 10) B-1 as a styrene resin and C-1 or C- as a modified olefin resin.
3, and using Y-1 or Y-4 as a compatibilizer,
Pellets of the thermoplastic resin composition were obtained in the same manner as in Example 6 except that the contents were changed to those shown in Table 5.

Comparative Examples 11-14 A-1 as vinyl chloride resin, B-2 as styrene resin, C-2 or C-3 as modified olefin resin, and Y-1 or Y as compatibilizer. -4 was used and the contents of the compositions shown in Table 6 were used, respectively, and pellets of the thermoplastic resin composition were obtained in the same manner as in Example 9.

Using the pellets of the thermoplastic resin composition obtained in the above Examples and Comparative Examples, test pieces were molded by a 5 ounce injection molding machine. At this time, the nozzle temperatures were set to Examples 1 to 5, 9 to 12, and Comparative Examples 1 to 6, 11 to 1.
No. 4, at 180 ° C., Examples 6 to 8 and Comparative Examples 7-1.
0 was set to 230 ° C. The following physical property tests were conducted using the molded test pieces.

1. Surface layer releasability Using the molded articles obtained in the above Examples and Comparative Examples, the surface layer releasability was measured by evaluating the releasability. That is, length 100 mm × width 150 mm × thickness 1.
Using a 5mm flat plate molded product, with the gate as the base point,
Two 5 cm incisions were made so as to form an angle of 30 ° and peeled from the gate side, and the peeling method was visually evaluated. The evaluation criteria were the following five-level visual evaluation. That is, the larger the value is, the more excellent the molded article is in the surface layer peeling resistance.

5 points: The molded product does not peel off from the gate side. 4 points: Less than 5 mm of the molded product peels from the gate side. 3 points: 5 mm or more and less than 2 cm of the molded product is peeled off from the gate side. 2 points: 2 cm or more and less than 5 cm of the molded product is peeled off from the gate side. 1 point: 5 cm or more of the molded product is peeled off from the gate side.

2. Impact strength Using the molded products obtained in the above Examples and Comparative Examples, A
The impact strength (kg · cm / cm (23 ° C)) was measured by the Izod impact test based on the STM D-256 standard.

3. Fluidity Using the molded articles obtained in the above Examples and Comparative Examples, 5
The fluidity of the molded product was evaluated by measuring the flow distance (mm) in a mosquito coiled incense-shaped mold having a thickness of 3 mm and a width of 10 mm using an ounce injection molding machine.

The results are shown in Tables 7 and 8.

[0097]

[Table 7]

[0098]

[Table 8]

From the results shown in the table, it was found that the molded product of the thermoplastic resin composition of the present invention was excellent in impact resistance, surface layer peeling resistance and fluidity.

[0100]

As is clear from the above description, the thermoplastic resin composition of the present invention has excellent fluidity during molding,
In addition, the molded product has excellent impact resistance and surface peeling resistance under high shear. This composition is used as a resin for injection molding and can exhibit excellent performance.

Claims (15)

[Claims] 1. A thermoplastic resin (X) other than an olefin resin (1 to 99 parts by weight) and a modified olefin resin (C).
A thermoplastic resin composition containing 0.1 to 50 parts by weight of a compatibilizing agent (Y) per 100 parts by weight of a base resin containing 99 to 1 part by weight of the compatibilizing agent (Y). Is a modified olefin polymer (D) 5
~ 95 parts by weight and modified vinyl chloride polymer (E) 95 ~
The modified olefin polymer (D) is selected from the group consisting of an amide group, a glycidyloxy group and a glycidyl group per 2 to 1000 repeating units of olefin. The modified vinyl chloride polymer (E) contains a structural unit having at least one reactive group, and the modified vinyl chloride polymer (E) has a group reactive with the reactive group contained in the modified olefin polymer (D). A thermoplastic resin composition containing the compound having a copolymerization component in an amount of 0.05 to 50% by weight. 2. The thermoplastic resin composition according to claim 1, wherein the modified olefin polymer (D) is an olefin polymer modified with a compound represented by the general formula (I). [Chemical 1] (In the formula, Ar represents an aromatic hydrocarbon group having 9 to 23 carbon atoms, which has at least one reactive group selected from the group consisting of a glycidyloxy group and a glycidyl group,
R represents a hydrogen atom or a methyl group. ) 3. The thermoplastic resin composition according to claim 1, wherein the modified vinyl chloride polymer (E) is a vinyl chloride polymer modified with a compound having a carboxyl group. 4. The thermoplastic resin (X) other than the olefin resin is at least one selected from the group consisting of vinyl chloride resin (A) and styrene resin (B). The thermoplastic resin composition according to any one of 3 above. 5. The thermoplastic resin composition according to claim 4, wherein the vinyl chloride resin (A) has an average degree of polymerization of 400 to 1500. 6. The methyl ethyl ketone-soluble component of the styrene resin (B) contains 10 to 60% by weight of at least one compound selected from the group consisting of vinyl cyanide compounds and alkyl methacrylate compounds as a copolymerization component. And the reduced viscosity of the soluble component is 0.2.
~ 0.9 dl / g (dimethylformamide solution, 30
6. The thermoplastic resin composition according to claim 4 or 5, which has a temperature of 0.3 g / dl). 7. The thermoplastic resin, wherein the styrene resin (B) is a mixture of a graft copolymer in an amount of 0 to 70 parts by weight, and the graft copolymer is a rubbery polymer 40. ~ 90% by weight
And 60 to 10% by weight of a monomer mixture, and the monomer mixture is a vinyl cyanide compound, an aromatic vinyl compound, an alkyl methacrylate compound, and a monomer copolymerizable with the compound. The thermoplastic resin composition according to any one of claims 4 to 6, which comprises at least one compound selected from the group consisting of monomers. 8. The thermoplastic resin composition according to claim 4, wherein the styrene-based resin (B) has a methyl ethyl ketone-soluble content of 30% by weight or more of α-methylstyrene. . 9. The thermoplastic resin composition according to claim 4, wherein the modified olefin resin (C) is a propylene polymer. 10. The thermoplastic resin composition according to claim 4, wherein the modified olefin resin (C) has a weight average molecular weight of 5,000 to 1,000,000. 11. The modified olefin resin (C) is an olefin resin containing a group reactive with a glycidyloxy group or a glycidyl group contained in the modified olefin polymer (D). 11. The thermoplastic resin composition according to any one of 1 to 10. 12. The olefin resin according to claim 4, wherein the modified olefin resin (C) is an olefin resin containing a group reactive with a reactive group of the modified vinyl chloride polymer (E). The thermoplastic resin composition according to any one of claims. 13. The thermoplastic resin composition according to claim 4, wherein the modified olefin resin (C) is an olefin resin containing a carboxyl group. 14. The thermoplastic resin composition according to claim 4, wherein the modified olefin resin (C) is an olefin resin containing an epoxy group. 15. The thermoplastic resin composition according to claim 1, which is used as an injection molding resin.